Tetra­carbonyl­(di­phenyl­di­thio­phosphinato-S,S')­rhenium(I)

The title compound consists of [Re(C₁₂H₁₀PS₂)(CO)₄] mol­ecules in which the Re atom is octahedrally coordinated by four carbonyl groups and two di­thio­phosphinate S atoms. The main coordination distortion is imposed by the ligand bite angle of 78.29 (4)°. The bidentate coordination of the di­thio­phosphinate ligand involves almost equal Re-S [2.5366 (15) and 2.5535 (14) Å] and P-S distances [2.0100 (19) and 2.0212 (19) Å].

S1. Comment

The dithiophosphinato ligand is a very versatile chelating ligand in transition metal coordination chemistry. Consequently, a great number of metal and organometallic complexes are known (Haiduc et al., 1995). However, the corresponding derivatives of carbonyl complexes of group 7 are rather scarce. This is surprising because they have been used as suitable precursors in the synthesis of dinuclear (Thiele et al., 1974a, and references therein) or cis-disubstituted complexes (Lidner & Berke, 1972). Additionally, structural knowledge of the carbonyl complexes of group 7 can be applied in comparative studies of other dithioligand complexes with interesting properties such as luminiscence; see Leirer et al., 1998. As a part of the study of the coordinative behaviour of the [Re(CO)₃]⁺ and [Re(CO)₄]⁺ moieties we have synthesized [Re(S₂PPh₂)(CO)₄] by a similar method to that of Lindner & Matejcek (1970).

The structure consists of isolated [Re(S₂PPh₂)(CO)₄] molecules with no unusually short contacts. The dithiophosphinate ligand links to rhenium in an almost symmetrical bidentate mode. The Re—S distances are close to those found in the dimeric [Re₂(µ-S₂PEt₂)₂(CO)₆] [2.535 (8)–2.570 (11) Å; Thiele et al., 1974a] but slightly longer than in dithiocarbamate analogues [Re{S₂CN(H)Ph}(CO)₃(PPh₃)₂] [2.512 (5) and 2.525 Å; Rossi et al., 1987], [Re{S₂CN(H)Tiaz}(CO)₂(PPh₃)] (Tiaz = thiazol-2-yl; Rossi et al., 1988) and the dithiocarboxylate [Re(S₂CPh)(CO)₄] (2.49 Å; Thiele & Liehr, 1971) or the trithiocarbonate [Re₄(CS₃)₂(CO)₁₆] (2.487–2.514 Å, Thiele et al., 1974b). The Re—C distances corresponding to carbonyl groups trans to the sulfur atoms are systematically shorter. In agreement with the latter, the corresponding C—O distances are slightly increased. Similar effects have been observed in [Mn(S₂PEt₂)(CO)₄] (Almond et al., 1995) and suggest some π-donor character of the dithiophosphinato ligand.

The P atom lies 0.532 (2) Å out of the plane defined by the rhenium and sulfur atoms and the two carbonyl groups trans to the dithiophosphinato ligand (Re/C3/O3/C4/O4/S1/S2, r.m.s. deviation = 0.017 Å). The chelation mode arranges a phenyl group almost parallel to the vector Re—C1—O1 (Fig. 1), whereby the shortest distances C1···C16 and C1···C11 [3.417 (10) and 3.497 (9) Å, respectively] are slightly longer than the double van der Waals radius (1.70 Å) of carbon (Spek, 2000). The resulting four-membered ring, ReS₂P, is not planar; the angles are S1—Re—S2 78.29 (4), P—S1—Re 85.52 (6), P—S2—Re 84.85 (6) and S1—P—S2 105.71 (8)°, and the fold angle about the S1···S2 vector is 26.47 (6)°.

The coordination polyhedron around the rhenium atom can be described as a slightly distorted octahedron, the main distortion being imposed by the ligand bite [S1—Re—S2 78.29 (4)°]. The P—S distances are practically identical and consistent with the bidentate character of the ligand. They are also close to those found in [Mn(S₂PEt₂)(CO)₄] [2.004 (4) and 2.008 (4) Å; Almod et al., 1995].

Related literature

For related literature, see: Almond et al. (1995); Haiduc et al. (1995); Leirer et al. (1998); Lidner & Berke (1972); Rossi et al. (1987, 1988); Spek (2000); Thiele & Liehr (1971); Thiele et al. (1974a, 1974b).

S2. Experimental

The title compound was obtained by a similar method to that reported by Lindner & Matejcek (1970) using [ReBr(CO)₅] and HS₂PPh₂ in toluene. Single crystals of the compound were obtained by storing the mother liquor at 269 K for some days. Analysis found: C 33.1, H 1.9, S 10.4%. C₁₆H₁₀O₄PS₂Re requires, C 33.2, H 1.7, S 11.0%. Mass spectrum (FAB-NBA; m/z, %): |M|⁺ 453 (31), |M—CO|⁺ 424 (100), |M-2CO|⁺ 396 (19), |M-3CO|⁺ 368 (17), |M-4CO|⁺ 340 (11). IR(Raman) spectrum (KBr, cm^-1): 1925 s(1927 s), 1983m(1976 s), 2004m (1991m), 2102 s(2100 s) ν(CO); 571 s(-) ν_asym(PS₂); 493 s(495 s) ν_sym(PS₂). ¹³C NMR spectrum (CDCl₃, p.p.m.): 184.4, 184.2 δ(CO). δ(³¹P) = 124.3 p.p.m..

S3. Refinement

H atoms were geometrically calculated and refined using a riding model. The largest difference peak (1.36 e ų) lies 0.94 Šfrom the Re atom.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. [Re(S2PPh2)(CO)4] as drawn by ZORTEP (Zsolnai & Huttner, 1994). Atoms represented as displacement ellipsoids are drawn at the 30% probability level.

Diphenyldithiophosphinato-tetracarbonylrhenium(I)

Crystal data

[Re(C12H10PS2)(CO)4]	F(000) = 2080
Mr = 547.53	Dx = 2.000 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 16.1160 (1) Å	µ = 7.02 mm^−1
b = 12.8286 (2) Å	T = 293 K
c = 17.5930 (3) Å	Prism, light brown
V = 3637.28 (9) Å^3	0.20 × 0.15 × 0.10 mm
Z = 8

Data collection

CCD area detector diffractometer	4518 independent reflections
Radiation source: fine-focus sealed tube	3181 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
ϕ and ω scans	θmax = 28.3°, θmin = 2.3°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −21→21
Tmin = 0.271, Tmax = 0.551	k = −13→17
23344 measured reflections	l = −23→21

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0438P)^2] where P = (Fo^2 + 2Fc^2)/3
4518 reflections	(Δ/σ)max = 0.002
217 parameters	Δρmax = 1.36 e Å^−3
0 restraints	Δρmin = −3.52 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Re	0.311151 (13)	0.025387 (16)	−0.661550 (12)	0.03976 (9)
S1	0.34950 (10)	−0.03238 (10)	−0.52821 (9)	0.0493 (3)
S2	0.32155 (9)	0.19964 (10)	−0.59206 (8)	0.0502 (3)
P	0.31646 (8)	0.11232 (10)	−0.49654 (7)	0.0382 (3)
O1	0.1201 (3)	0.0140 (5)	−0.6340 (4)	0.0928 (17)
O2	0.5010 (3)	0.0495 (4)	−0.6936 (4)	0.0903 (16)
O3	0.3092 (2)	−0.1966 (3)	−0.7265 (3)	0.0617 (12)
O4	0.2643 (4)	0.1141 (4)	−0.8171 (3)	0.0886 (17)
C1	0.1895 (4)	0.0176 (5)	−0.6418 (5)	0.0591 (17)
C2	0.4330 (5)	0.0391 (4)	−0.6818 (4)	0.0553 (15)
C3	0.3103 (3)	−0.1135 (5)	−0.7022 (3)	0.0474 (13)
C4	0.2826 (4)	0.0827 (5)	−0.7595 (4)	0.0581 (15)
C11	0.2133 (3)	0.1158 (4)	−0.4577 (3)	0.0403 (11)
C12	0.1807 (3)	0.2120 (5)	−0.4361 (4)	0.0525 (14)
H12	0.2119	0.2724	−0.4419	0.063*
C13	0.1022 (4)	0.2166 (6)	−0.4063 (4)	0.0648 (17)
H13	0.0805	0.2807	−0.3918	0.078*
C14	0.0557 (4)	0.1301 (7)	−0.3976 (4)	0.075 (2)
H14	0.0027	0.1351	−0.3772	0.090*
C15	0.0868 (4)	0.0344 (6)	−0.4189 (5)	0.080 (2)
H15	0.0545	−0.0251	−0.4130	0.097*
C16	0.1651 (4)	0.0266 (5)	−0.4489 (4)	0.0567 (15)
H16	0.1859	−0.0381	−0.4634	0.068*
C21	0.3829 (3)	0.1644 (4)	−0.4238 (3)	0.0398 (11)
C22	0.3623 (4)	0.1583 (6)	−0.3487 (3)	0.0602 (17)
H22	0.3122	0.1283	−0.3341	0.072*
C23	0.4165 (4)	0.1970 (6)	−0.2942 (4)	0.080 (2)
H23	0.4016	0.1954	−0.2431	0.096*
C24	0.4909 (5)	0.2370 (6)	−0.3149 (4)	0.075 (2)
H24	0.5270	0.2623	−0.2780	0.090*
C25	0.5127 (4)	0.2402 (5)	−0.3878 (5)	0.077 (2)
H25	0.5642	0.2671	−0.4013	0.092*
C26	0.4597 (4)	0.2041 (5)	−0.4436 (4)	0.0656 (17)
H26	0.4757	0.2064	−0.4944	0.079*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Re	0.05144 (14)	0.04501 (14)	0.02284 (14)	0.00279 (9)	−0.00006 (8)	−0.00227 (8)
S1	0.0744 (10)	0.0412 (7)	0.0324 (8)	0.0110 (6)	−0.0022 (7)	0.0023 (6)
S2	0.0835 (10)	0.0417 (7)	0.0254 (8)	0.0021 (7)	0.0016 (7)	0.0042 (5)
P	0.0522 (7)	0.0410 (6)	0.0215 (7)	0.0024 (5)	−0.0011 (5)	0.0019 (5)
O1	0.047 (3)	0.139 (5)	0.092 (4)	0.001 (3)	0.001 (3)	−0.021 (3)
O2	0.067 (3)	0.090 (4)	0.115 (5)	−0.004 (3)	0.017 (3)	0.004 (3)
O3	0.076 (3)	0.056 (2)	0.054 (3)	−0.006 (2)	−0.004 (2)	−0.016 (2)
O4	0.153 (5)	0.084 (3)	0.029 (3)	0.023 (3)	−0.023 (3)	0.003 (2)
C1	0.061 (4)	0.066 (4)	0.050 (4)	0.008 (3)	−0.001 (3)	−0.007 (3)
C2	0.067 (4)	0.052 (3)	0.047 (4)	−0.004 (3)	0.009 (3)	−0.003 (3)
C3	0.052 (3)	0.062 (3)	0.028 (3)	−0.001 (3)	−0.004 (2)	0.001 (3)
C4	0.085 (4)	0.053 (4)	0.037 (4)	0.005 (3)	−0.003 (3)	−0.010 (3)
C11	0.050 (3)	0.048 (3)	0.023 (3)	0.002 (2)	−0.005 (2)	0.002 (2)
C12	0.052 (3)	0.059 (3)	0.046 (4)	0.006 (3)	−0.008 (3)	−0.004 (3)
C13	0.055 (4)	0.080 (4)	0.059 (5)	0.016 (3)	−0.005 (3)	−0.009 (3)
C14	0.050 (4)	0.111 (6)	0.064 (5)	0.005 (4)	0.006 (3)	0.004 (4)
C15	0.068 (5)	0.090 (5)	0.084 (6)	−0.021 (4)	0.013 (4)	0.015 (4)
C16	0.060 (3)	0.059 (4)	0.051 (4)	−0.002 (3)	0.006 (3)	0.006 (3)
C21	0.046 (3)	0.044 (3)	0.029 (3)	0.006 (2)	0.000 (2)	−0.005 (2)
C22	0.047 (3)	0.103 (5)	0.030 (3)	0.008 (3)	−0.003 (2)	−0.007 (3)
C23	0.075 (5)	0.130 (6)	0.036 (4)	0.030 (4)	−0.011 (3)	−0.024 (4)
C24	0.071 (4)	0.087 (5)	0.068 (5)	0.018 (4)	−0.026 (4)	−0.038 (4)
C25	0.062 (4)	0.088 (5)	0.080 (6)	−0.018 (3)	−0.005 (4)	−0.016 (4)
C26	0.064 (4)	0.089 (5)	0.044 (4)	−0.016 (3)	0.000 (3)	−0.006 (3)

Geometric parameters (Å, º)

Re—C3	1.920 (6)	O4—C4	1.130 (7)
Re—C4	1.929 (7)	C1—C16	3.417 (10)
Re—C1	1.993 (7)	C1—C11	3.497 (9)
Re—C2	2.004 (7)	C1—C15	4.261 (12)
Re—S1	2.5366 (15)	C1—C12	4.396 (10)
Re—S2	2.5535 (14)	C1—C14	5.018 (10)
S1—P	2.0100 (19)	C1—C13	5.065 (10)
S2—P	2.0212 (19)	C11—C16	1.392 (7)
P—C21	1.798 (5)	C11—C12	1.393 (8)
P—C11	1.799 (5)	C12—C13	1.371 (8)
O1—C1	1.128 (7)	C13—C14	1.346 (9)
O1—C16	3.340 (10)	C14—C15	1.378 (10)
O1—C11	3.686 (8)	C15—C16	1.372 (9)
O1—C15	3.831 (11)	C21—C22	1.365 (7)
O1—C12	4.419 (9)	C21—C26	1.383 (7)
O1—C14	4.538 (10)	C22—C23	1.389 (9)
O1—C13	4.784 (9)	C23—C24	1.354 (10)
O2—C2	1.123 (8)	C24—C25	1.330 (10)
O3—C3	1.148 (7)	C25—C26	1.382 (9)
C3—Re—C4	91.1 (2)	C11—C1—C14	31.83 (13)
C3—Re—C1	90.7 (2)	C15—C1—C14	14.30 (13)
C4—Re—C1	86.6 (3)	C12—C1—C14	28.17 (12)
C3—Re—C2	91.3 (2)	O1—C1—C13	69.3 (5)
C4—Re—C2	92.4 (3)	Re—C1—C13	113.0 (3)
C1—Re—C2	177.8 (3)	C16—C1—C13	30.58 (14)
C3—Re—S1	94.30 (17)	C11—C1—C13	24.66 (12)
C4—Re—S1	174.57 (18)	C15—C1—C13	27.63 (13)
C1—Re—S1	93.6 (2)	C12—C1—C13	14.57 (10)
C2—Re—S1	87.2 (2)	C14—C1—C13	15.33 (11)
C3—Re—S2	172.41 (17)	O2—C2—Re	178.1 (6)
C4—Re—S2	96.28 (18)	O3—C3—Re	179.5 (5)
C1—Re—S2	91.43 (19)	O4—C4—Re	178.0 (6)
C2—Re—S2	86.80 (17)	C16—C11—C12	119.2 (5)
S1—Re—S2	78.29 (4)	C16—C11—P	122.5 (4)
P—S1—Re	85.52 (6)	C12—C11—P	118.3 (4)
P—S2—Re	84.85 (6)	C16—C11—C1	75.2 (4)
C21—P—C11	105.7 (2)	C12—C11—C1	122.0 (4)
C21—P—S1	112.49 (17)	P—C11—C1	74.9 (2)
C11—P—S1	111.92 (18)	C16—C11—O1	64.8 (4)
C21—P—S2	111.22 (18)	C12—C11—O1	112.9 (4)
C11—P—S2	109.86 (18)	P—C11—O1	92.7 (2)
S1—P—S2	105.71 (8)	C1—C11—O1	17.82 (13)
C1—O1—C16	84.3 (5)	C13—C12—C11	119.3 (6)
C1—O1—C11	71.5 (5)	C13—C12—C1	111.7 (4)
C16—O1—C11	22.15 (13)	C11—C12—C1	42.4 (3)
C1—O1—C15	104.8 (6)	C13—C12—O1	97.0 (4)
C16—O1—C15	20.62 (15)	C11—C12—O1	50.2 (3)
C11—O1—C15	37.00 (14)	C1—C12—O1	14.71 (10)
C1—O1—C12	81.5 (5)	C14—C13—C12	121.4 (6)
C16—O1—C12	32.45 (14)	C14—C13—O1	71.4 (4)
C11—O1—C12	16.88 (11)	C12—C13—O1	66.5 (4)
C15—O1—C12	38.13 (15)	C14—C13—C1	80.4 (4)
C1—O1—C14	108.9 (5)	C12—C13—C1	53.8 (4)
C16—O1—C14	30.71 (15)	O1—C13—C1	12.75 (9)
C11—O1—C14	37.37 (13)	C13—C14—C15	120.1 (6)
C15—O1—C14	16.31 (14)	C13—C14—O1	92.2 (4)
C12—O1—C14	30.64 (12)	C15—C14—O1	51.3 (4)
C1—O1—C13	98.0 (5)	C13—C14—C1	84.3 (4)
C16—O1—C13	33.95 (14)	C15—C14—C1	49.8 (4)
C11—O1—C13	29.22 (11)	O1—C14—C1	12.28 (9)
C15—O1—C13	29.21 (14)	C16—C15—C14	120.3 (6)
C12—O1—C13	16.53 (10)	C16—C15—O1	59.1 (4)
C14—O1—C13	16.33 (11)	C14—C15—O1	112.4 (5)
O1—C1—Re	176.8 (7)	C16—C15—C1	44.3 (4)
O1—C1—C16	76.5 (5)	C14—C15—C1	115.9 (5)
Re—C1—C16	106.6 (3)	O1—C15—C1	14.83 (11)
O1—C1—C11	90.7 (5)	C15—C16—C11	119.7 (6)
Re—C1—C11	92.1 (3)	C15—C16—O1	100.3 (5)
C16—C1—C11	23.19 (13)	C11—C16—O1	93.1 (4)
O1—C1—C15	60.4 (5)	C15—C16—C1	119.4 (5)
Re—C1—C15	122.7 (3)	C11—C16—C1	81.6 (4)
C16—C1—C15	16.29 (15)	O1—C16—C1	19.18 (13)
C11—C1—C15	34.10 (15)	C22—C21—C26	118.9 (5)
O1—C1—C12	83.8 (5)	C22—C21—P	121.5 (4)
Re—C1—C12	98.5 (2)	C26—C21—P	119.4 (4)
C16—C1—C12	32.88 (14)	C21—C22—C23	119.7 (6)
C11—C1—C12	15.59 (11)	C24—C23—C22	120.4 (7)
C15—C1—C12	37.02 (14)	C25—C24—C23	120.3 (6)
O1—C1—C14	58.8 (5)	C24—C25—C26	120.8 (7)
Re—C1—C14	123.9 (3)	C25—C26—C21	119.8 (6)
C16—C1—C14	24.64 (14)